CN101542690B - Aqueous dispersion for chemical mechanical polishing and method of chemical mechanical polishing of semiconductor device - Google Patents
Aqueous dispersion for chemical mechanical polishing and method of chemical mechanical polishing of semiconductor device Download PDFInfo
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- CN101542690B CN101542690B CN2008800005313A CN200880000531A CN101542690B CN 101542690 B CN101542690 B CN 101542690B CN 2008800005313 A CN2008800005313 A CN 2008800005313A CN 200880000531 A CN200880000531 A CN 200880000531A CN 101542690 B CN101542690 B CN 101542690B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Abstract
The present invention provides an aqueous dispersion for chemical mechanical polishing which contains (A) 0.1-4 mass% colloidal silica having an average particle diameter of 10-100 nm and (B) 0.1-3 mass% at least one member selected among monoammonium phosphate, diammonium phosphate, and ammonium hydrogen sulfate and in which the proportion of the ingredient (A) to the ingredient (B), (A)/(B), is1-3 by mass. It has a pH of 4-5. With the dispersion, a surface to be polished which is constituted of two or more members selected among a polysilicon film, silicon nitride film, and silicon oxide film can be simultaneously polished.
Description
Technical field
The present invention relates to make aqueous dispersion for chemical mechanical polishing used in the semiconductor device and used the chemical and mechanical grinding method of this aqueous dispersion for chemical mechanical polishing.
Background technology
As a rule, cmp (below be also referred to as " CMP ".) can be exposed diversified materials such as polysilicon film (Polycrystalline Silicon film), monocrystalline silicon membrane, silicon oxide film, silicon nitride film, aluminium, tungsten, copper by abradant surface.
In the past, use with a kind of aqueous dispersion for chemical mechanical polishing in the middle of the above-mentioned material as target (target) (below be also referred to as " slurry ".), this material use CMP as target is removed.But, if a great difference is arranged with the grinding rate ratio of other materials, then will over-lapping as the material of target, thus cause defectives such as depression (dishing), corrosion sometimes.In addition, must select aqueous dispersion for chemical mechanical polishing and utilize CMP to remove, do the problem that all can have productivity ratio to reduce in any case according to every kind of material as target.
In recent years, be accompanied by the structure variation of semiconductor equipment, require polysilicon film, silicon oxide film and three kinds of materials of silicon nitride film are ground simultaneously.In order to grind this three kinds of materials simultaneously, must provide a kind of substantially the same aqueous dispersion for chemical mechanical polishing of grinding rate that makes each film.
Up to now, for example open flat 11-176773 communique, spy the spy and open 2001-7061 communique, spy and open that 2001-35820 communique, spy are opened the 2002-190458 communique, the spy opens in 2004-269577 communique etc., the grinding rate that proposed to make silicon nitride film and silicon oxide film is than the aqueous dispersion for chemical mechanical polishing that is roughly 1.But still not existing can be with polysilicon film, silicon oxide film and silicon nitride film while and the aqueous dispersion for chemical mechanical polishing that grinds with identical grinding rate.
Summary of the invention
The objective of the invention is to, provide a kind of and polysilicon film, silicon nitride film and silicon oxide film are had enough grinding rates and make the substantially the same aqueous dispersion for chemical mechanical polishing of the grinding rate of each film and used the chemical and mechanical grinding method of its semiconductor device.
Aqueous dispersion for chemical mechanical polishing of the present invention, pH is 4～5, be used for simultaneously to by be selected from polysilicon film, silicon nitride film and silicon oxide film form more than 2 kinds ground by abradant surface, it contains: (A) of 0.1～4 quality %: the colloidal silica with average grain diameter of 10nm～100nm; And 0.1～3 quality % (B): be selected from least a in ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the ammonium hydrogen sulfate, the mass ratio (A)/(B) of described (A) composition and described (B) composition is 1～3.
Aqueous dispersion for chemical mechanical polishing of the present invention can also contain and is selected from least a in nitric acid, sulfuric acid, carbonic acid, lactic acid, formic acid, benzoic acid, citric acid, tartaric acid, malic acid, malonic acid, fumaric acid, maleic acid, butanedioic acid, oxalic acid, phthalic acid, adipic acid, decanedioic acid and their ammonium salt.
In the aqueous dispersion for chemical mechanical polishing of the present invention, the grinding rate of polysilicon film and silicon oxide film can be 0.9～1.1 than the grinding rate of (polysilicon film/silicon oxide film) and silicon nitride film and silicon oxide film than (silicon nitride film/silicon oxide film).
The chemical and mechanical grinding method of semiconductor device of the present invention is characterised in that, use any one above-mentioned aqueous dispersion for chemical mechanical polishing, simultaneously to by be selected from polysilicon film, silicon nitride film and the silicon oxide film form more than 2 kinds ground by abradant surface.
Aqueous dispersion for chemical mechanical polishing of the present invention has enough grinding rates to polysilicon film, silicon nitride film and silicon oxide film, can make the grinding rate of each film substantially the same.Like this, just can be side by side to by be selected from polysilicon film, silicon nitride film and the silicon oxide film form more than 2 kinds ground by abradant surface.In addition, if use aqueous dispersion for chemical mechanical polishing of the present invention, when then the equipment with polysilicon film, silicon nitride film and silicon oxide film being carried out cmp, then need not to change slurry on the way, remove and can grind continuously according to grinding object.In addition, because grinding rate is all substantially the same concerning any film, therefore as long as the control milling time just can be set at required thickness at an easy rate.
Description of drawings
Fig. 1 schematically shows the profile of evaluation used in first experimental example with substrate.
Fig. 2 schematically shows the profile of evaluation used in first experimental example with substrate.
Fig. 3 schematically shows the profile of evaluation used in first experimental example with substrate.
Fig. 4 schematically shows the profile of evaluation used in second experimental example with substrate.
Fig. 5 schematically shows the profile of evaluation used in second experimental example with substrate.
Fig. 6 schematically shows the profile of evaluation used in second experimental example with substrate.
Embodiment
Below, embodiments of the present invention are described.
And the present invention is not limited to following execution mode, is also contained in the various variation of implementing in the scope that does not change purport of the present invention.
1. aqueous dispersion for chemical mechanical polishing
Aqueous dispersion for chemical mechanical polishing of the present invention contains: (A) of 0.1～4 quality %: the colloidal silica with average grain diameter of 10nm～100nm; And 0.1～3 quality % (B): be selected from least a in ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the ammonium hydrogen sulfate, the mass ratio (A)/(B) of described (A) composition and described (B) composition is 1～3, and pH is 4～5, for simultaneously to by be selected from polysilicon film, silicon nitride film and the silicon oxide film form more than 2 kinds ground by abradant surface and use.Below, each contained in the aqueous dispersion for chemical mechanical polishing to present embodiment composition is described in detail.
1.1 (A) colloidal silica
The aqueous dispersion for chemical mechanical polishing of present embodiment contains colloidal silica as abrasive particle.The average grain diameter of this colloidal silica is preferably 10nm～100nm, and more preferably 20nm～90nm is preferably 30nm～80nm especially.If the average grain diameter of colloidal silica is in the scope of 10nm～100nm, then owing to good as the storage stability of aqueous dispersion for chemical mechanical polishing, the performance (grinding rate etc.) after therefore can keeping just having prepared.If the average grain diameter of colloidal silica is less than 10nm, then the grinding rate owing to polysilicon film, silicon nitride film and silicon oxide film becomes too small, therefore can't be practical.On the other hand, if the average grain diameter of colloidal silica surpasses 100nm, then colloidal silica will mechanically grind silicon oxide film, and the grinding rate of silicon oxide film becomes excessive, thus balance.
The average grain diameter of colloidal silica for example utilizes dynamic light scattering formula LB550 (Horiba Ltd's system) to use dynamic light scattering determination.This average grain diameter is represented the primary particle cohesion and the offspring diameter of formation.Because colloidal silica can form offspring usually in abradant surface generation mechanical abrasive action, therefore with the object of offspring diameter as evaluation.
The quality of the aqueous dispersion for chemical mechanical polishing of the addition of colloidal silica when using is preferably 0.1～4 quality %, and more preferably 0.2～4 quality % is preferably 0.3～3.9 quality % especially.If the addition of colloidal silica then can't obtain enough grinding rates less than 0.1 quality %, thereby can't be practical.On the other hand, if the addition of colloidal silica surpasses 4 quality %, then colloidal silica will mechanically grind silicon oxide film, makes the grinding rate of silicon oxide film become excessive.Defective when in addition, producing cut etc. sometimes and grind.
And said in this specification " enough grinding rates " is meant that specifically grinding rate is more than 20nm/ minute.
1.2 (B) acid ammonium salt
The aqueous dispersion for chemical mechanical polishing of present embodiment contains at least a ammonium salt that is selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the ammonium hydrogen sulfate.If add these acid ammonium salts, just can increase grinding rate to silicon nitride film.
Can infer, ammonium dihydrogen phosphate and diammonium hydrogen phosphate utilize phosphate anion to the chemical grinding effect of silicon nitride film and ammonium radical ion to the cooperative effect between the chemical grinding effect of silicon nitride film, can increase grinding rate to silicon nitride film.
Can infer, ammonium hydrogen sulfate utilize sulfate ion to the chemical grinding effect of silicon nitride film and ammonium radical ion to the cooperative effect between the chemical grinding effect of silicon nitride film, can increase grinding rate to silicon nitride film.
These acid ammonium salts can be used alone, and perhaps are used in combination two or more.
The quality of the aqueous dispersion for chemical mechanical polishing of the addition of these acid ammonium salts when using is preferably 0.1～3 quality %, and more preferably 0.2～2.5 quality % is preferably 0.3～1.3 quality % especially.If the addition of these acid ammonium salts less than 0.1 quality %, then reduces owing to grinding rate significantly, therefore can't be practical.On the other hand, if the addition of these acid ammonium salts surpasses 3 quality %, even then further increase the addition of acid ammonium salt, it is big that the grinding rate of silicon nitride film can not become basically yet, and the stability of aqueous dispersion for chemical mechanical polishing reduces, and is therefore not ideal enough.
In the aqueous dispersion for chemical mechanical polishing of present embodiment, (A) colloidal silica is 1～3 with (B) mass ratio of ammonium salt (A)/(B).More preferably 1.3～2.8, be preferably 1.5～2.5 especially.If mass ratio is in this scope, then can make the grinding rate of polysilicon film, silicon nitride film and silicon oxide film substantially the same.Like this, just can obtain to be suitable for the aqueous dispersion for chemical mechanical polishing that simultaneously these films ground.If mass ratio (A)/(B) is less than 1, then because mechanical abrasive action diminishes, therefore the balance of forfeiture and cmp effect just can't make the grinding rate of polysilicon film, silicon nitride film and silicon oxide film substantially the same.On the other hand,,, thereby make the grinding rate of silicon oxide film increase, therefore can't make the grinding rate of polysilicon film, silicon nitride film and silicon oxide film substantially the same then because mechanical abrasive action becomes big if mass ratio (A)/(B) surpasses 3.
1.3pH
The pH of the aqueous dispersion for chemical mechanical polishing of present embodiment is more than 4 below 5.If pH is in this scope, then can make the grinding rate of polysilicon film, silicon nitride film and silicon oxide film substantially the same.PH can utilize the addition of (A) composition and (B) composition and acid described later and alkali to adjust.The scope of preferred pH is more than 4.2 below 4.8.If pH is made as less than 4, then, make the grinding rate of silicon nitride film and silicon oxide film become big and balance owing to can't increase the grinding rate of polysilicon film, therefore can't realize the purpose of the present application.On the other hand,, then, make the grinding rate of polysilicon film become big and balance, therefore can't realize the purpose of the present application owing to can't increase the grinding rate of silicon nitride film and silicon oxide film if make pH greater than 5.
Said, because the grinding rate of the pH of the aqueous dispersion for chemical mechanical polishing of present embodiment and polysilicon film, silicon nitride film and silicon oxide film is closely related, therefore must critically control.So the aqueous dispersion for chemical mechanical polishing of present embodiment also can be to use the buffer solution of citrate buffer solution, phosphate buffer etc.
1.4 other additive
The aqueous dispersion for chemical mechanical polishing of present embodiment can add following additive as required.
1.4.1 acid or its ammonium salt
The aqueous dispersion for chemical mechanical polishing of present embodiment can add acid or its ammonium salt as required.As acid or its ammonium salt, can enumerate nitric acid, sulfuric acid, carbonic acid, lactic acid, formic acid, benzoic acid, citric acid, tartaric acid, malic acid, malonic acid, fumaric acid, maleic acid, butanedioic acid, oxalic acid, phthalic acid, adipic acid, decanedioic acid or their ammonium salt.By adding these acid or its ammonium salts, just can increase the grinding rate of silicon nitride film and silicon oxide film.So just can realize fine setting with the grinding rate of polysilicon film.
1.4.2 surfactant
The aqueous dispersion for chemical mechanical polishing of present embodiment can add surfactant as required.As surfactant, for example can enumerate cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant.
As cationic surfactant, for example can enumerate aliphat amine salt, aliphat ammonium salt etc.
As the anionic surfactant, for example can enumerate carboxylate, sulfonate, sulfuric acid, phosphate ester salt etc.As carboxylate, can enumerate fatty acid soaps, alkyl ether carboxy acid salt etc.As sulfonate, can enumerate alkylbenzenesulfonate, alkylnaphthalene sulfonate, alpha-alkene sulfonate etc.As sulfuric acid, for example can enumerate higher alcohol sulfate salt, alkyl sulfate salt etc.As phosphate, for example can enumerate alkyl phosphate etc.
As nonionic surfactant, for example can enumerate ether type surfactant, Etheric ester type surfactant, ester type surfactant, acetylene is surfactant etc.As the Etheric ester type surfactant, for example can enumerate the APEO of glyceride etc.As ester type surfactant, for example can enumerate cithrol, glyceride, Isosorbide Dinitrate etc.As acetylene is surfactant, for example can enumerate the ethylene oxide adduct of acetylene alcohol, acetylenediol, acetylenediol.
As amphoteric surfactant, for example can enumerate betaine is surfactant.
These surfactants can be used alone, and perhaps are used in combination two or more.
In the middle of these surfactants, preferred anionic surfacant, preferred especially sulfonate.In addition, in the middle of sulfonate, preferred alkyl benzene sulfonate, preferred especially dodecyl benzene sulfonate.
The quality of the aqueous dispersion for chemical mechanical polishing of the addition of surfactant when using is preferably below the 1 quality %, more preferably 0.001～0.1 quality %.If the addition of surfactant is in the above-mentioned scope, then can silicon nitride film is ground remove after, obtain level and smooth by abradant surface.
1.4.3 acid or alkali
The aqueous dispersion for chemical mechanical polishing of present embodiment can add acid or alkali as required.The pH of the aqueous dispersion for chemical mechanical polishing of present embodiment is necessary for more than 4 below 5 as mentioned above.Here can use acid and alkali for the purpose of the pH that adjusts aqueous dispersion for chemical mechanical polishing.
As described acid, for example can enumerate above-mentioned organic acid or inorganic acid in addition.
As organic acid, for example can enumerate p-methyl benzenesulfonic acid, DBSA, isoprene sulfonic acid, gluconic acid, glycolic etc.
As described alkali, can enumerate organic base or inorganic base.
As organic base, for example can enumerate tetramethyl hydroxide (TetramethylHydroxide) etc.
As inorganic base, for example can enumerate alkali-metal hydroxide.Specifically, can enumerate NaOH, potassium hydroxide, rubidium hydroxide, cesium hydroxide etc.
1.4.4 water soluble polymer
The aqueous dispersion for chemical mechanical polishing of present embodiment can add water soluble polymer as required.Water soluble polymer has and is adsorbed in the function that abrasion friction is reduced.Like this, if add water soluble polymer, just can suppress the generation of caving in, corroding.
As water soluble polymer, can enumerate polyacrylamide, polyacrylic acid, polyvinyl alcohol, PVP, hydroxyethylcellulose etc.
The addition of water soluble polymer can be adjusted into and make the viscosity of aqueous dispersion for chemical mechanical polishing less than 2mPas.The viscosity of aqueous dispersion for chemical mechanical polishing of the present invention is decided by the weight average molecular weight and the addition of water soluble polymer basically, therefore can adjust in the balance of considering them.If the viscosity of aqueous dispersion for chemical mechanical polishing surpasses 2mPas, then have the situation that grinding rate reduces, in addition, it is too high that viscosity becomes, sometimes can't be on emery cloth the mechanical polishing aqueous dispersion of providing chemical stably.Consequently, produce the temperature rising of emery cloth or grind inequality (deterioration of internal homogeneity) etc., thereby produce the deviation of grinding rate or depression sometimes.
1.4.5 anticorrosive
Used anticorrosive in the aqueous dispersion for chemical mechanical polishing as present embodiment for example can be enumerated BTA and derivative thereof.Here, so-called benzotriazole derivatives is meant the material after the hydrogen atom more than 1 or 2 that BTA is had replaces with for example carboxyl, methyl, amino, hydroxyl etc.As benzotriazole derivatives, can enumerate 4-carboxyl benzotriazole and salt thereof, 7-carboxyl benzotriazole and salt thereof, BTA butyl ester, 1-hydroxymethyl BTA or I-hydroxybenzotriazole etc.
The quality of the aqueous dispersion for chemical mechanical polishing of the addition of anticorrosive when using is preferably below the 1 quality %, more preferably 0.001～0.1 quality %.
1.5 the compound method of aqueous dispersion for chemical mechanical polishing
The aqueous dispersion for chemical mechanical polishing of present embodiment can or disperse described each preparation that becomes to assign to by dissolving in the water equal solvent.Dissolving or process for dispersing are not particularly limited, so long as can dissolve equably, disperse, no matter are which kind of method can be used then.In addition, order by merging or the mixed method for each composition also is not particularly limited.
The aqueous dispersion for chemical mechanical polishing of present embodiment also can be mixed with the stoste of concentrated type, and use water equal solvent dilution back in use.
1.6 grinding rate ratio
The polysilicon film of the aqueous dispersion for chemical mechanical polishing of present embodiment and the grinding rate of silicon oxide film can be 0.9～1.1 than the grinding rate of (polysilicon film/silicon oxide film) and silicon nitride film and silicon oxide film than (silicon nitride film/silicon oxide film).
If the grinding rate of polysilicon film and silicon oxide film is than being in 0.9～1.1 the scope, then can be with by polysilicon film with silica is film formed is side by side ground with roughly the same speed by abradant surface.
If the grinding rate of silicon nitride film and silicon oxide film is than being in 0.9～1.1 the scope, then can be simultaneously with roughly the same speed to by silicon nitride film with silica is film formed is ground by abradant surface.
So, if both sides' grinding rate all is in 0.9～1.1 the scope, then can be simultaneously with roughly the same speed to being ground by abradant surface by polysilicon film, silicon nitride film and silica are film formed, therefore can be with by the abradant surface planarization.
2. the manufacture method of chemical and mechanical grinding method and semiconductor device
The chemical and mechanical grinding method of present embodiment and the manufacture method of semiconductor device are described.
2.1 chemical and mechanical grinding method
The Ginding process that has used the semiconductor substrate of aqueous dispersion for chemical mechanical polishing of the present invention is that the grinding pad of aqueous dispersion for chemical mechanical polishing on grinding plate supplied with, make it and contacted, make by abradant surface and grinding pad and relatively move and grind by abradant surface.As lapping device, can use to have anchor clamps that keep semiconductor substrate and the common grinding device that is pasted with the grinding plate of grinding pad.As grinding pad, can use common nonwoven fabrics, polyurathamc, porous fluoride resin etc.In grinding, with pump etc. continuously to the mechanical polishing aqueous dispersion of grinding pad providing chemical.Be not particularly limited for this quantity delivered, however the state that preferably keeps the total surface of grinding pad to be covered by grinding agent.Preferably after will grinding semiconductor substrate after finishing and fully cleaning, use spinner (spin drier) etc. will be attached to water droplet on the semiconductor substrate and shake off and make its drying with flowing water.
As handled object, can enumerate have by be selected from polysilicon film, silicon nitride film and the silicon oxide film form more than 2 kinds by the semiconductor substrate of abradant surface.
For example, aqueous dispersion for chemical mechanical polishing of the present invention can be used for trench isolations (STI).In the past, in trench isolations, used following method, that is, utilize CMP to remove silicon oxide film, and on silicon nitride film, stopped to grind, made the silicon nitride film dissolving and etching with hot phosphoric acid.But, if use aqueous dispersion for chemical mechanical polishing of the present invention, then not only can grind continuously, and also can grind continuously silicon nitride film to silicon oxide film, need not stop CMP on the way, can realize the raising of production efficiency.
In addition, aqueous dispersion for chemical mechanical polishing of the present invention can also be used for having by three kinds of polysilicon film, silicon nitride film and silicon oxide films form by the semiconductor device of abradant surface.Because grinding rate is all identical basically for film arbitrarily, therefore can when always guaranteeing flatness, carry out cmp.In addition, also need not grind object and select slurry, clean also, therefore can realize the raising of production efficiency as long as once according to each.
3. embodiment
Below, the present invention will be described to utilize embodiment, however the present invention is not subjected to any qualification of this embodiment.
3.1 the making of nonferromagnetic substance used substrate in estimating
At first, preparing by Diagonal Dimension is the semiconductor substrate that the silicon of 200mm is made.On this substrate, use CVD method or thermal oxidation method to form silicon oxide film, make thickness reach 1000nm.The substrate that so obtains is made as " substrate a ".
On described semiconductor substrate, use the CVD method to form silicon nitride film, make thickness reach 200nm.The substrate that so obtains is made as " substrate b ".
On described semiconductor substrate, use CVD method or thermal oxidation method to form silicon oxide film, make thickness reach 400nm., use CVD method form polysilicon film, make thickness reach 600nm thereafter.The substrate that so obtains is made as " substrate c ".
3.2 contain the preparation of the aqueous dispersion of inorganic abrasive particle
3.2.1 contain the aqueous dispersion of colloidal silica
Used colloidal silica has used Snowtex-O (average grain diameter 15nm), the Snowtex-OS (9nm) of PL-1 (average grain diameter 37nm), PL-2 (52nm), PL-3 (89nm), PL-20 (180nm) and the daily output chemical industrial company system of Japan chemical industrial company system in the embodiments of the invention.The average grain diameter of PL-1 series is to use dynamic light scattering mode LB550 (the hole field makes institute's corporate system) to measure.The average grain diameter of Snowtex-O and Snowtex-OS is expressed as catalogue (catalog) value.
3.2.2 the preparation of aqueous dispersion for chemical mechanical polishing
The ormal weight of inciting somebody to action the aqueous dispersion of being prepared in " 3.2.1 contains the preparation of the aqueous dispersion of colloidal silica " drops into volume 10000cm
3Polyethylene system bottle in, to wherein adding the described compound of table 1 or table 2 respectively, make it to reach the described content of table 1 or table 2, stir fully.With the filter filtration of aperture 5 μ ms, obtained the aqueous dispersion for chemical mechanical polishing of embodiment 1 to 8 and comparative example 1 to 10 thereafter.
3.3 cmp test
Use the aqueous dispersion for chemical mechanical polishing of embodiment 1 to 8 and comparative example 1 to 10, with substrate a, substrate b and substrate c as by abrasive body, with following＜grinding condition 1 carried out cmp.
＜grinding condition 1 〉
Lapping device: (strain) ebara corporatlon system, model " EPO-112 "
Grinding pad: Rodel Nitta (strain) system, " IC1000/K-Groove "
Aqueous dispersion for chemical mechanical polishing feed speed: 200mL/ minute
Platform rotating speed: 50rpm
Grinding head rotating speed: 55rpm
Grinding head pushing pressure: 4.2psi
3.3.1 the calculating of grinding rate ratio
Utilize light interference type film thickness gauge " NanoSpec 6100 " (Nanometrix Japan (strain) system) respectively to as being measured the preceding thickness of grinding in advance, under above-mentioned condition, carried out grinding in 60 seconds by the substrate a of abrasive body, substrate b and substrate c.After similarly using the light interference type film thickness gauge measure to grind by the thickness of abrasive body, obtain before grinding with grind after thickness poor, i.e. the thickness that reduces because of cmp.This operation is carried out 2 times, calculated the mean value of the thickness that reduces because of cmp.And, calculate grinding rate by the mean value and the milling time of the thickness that reduces because of cmp.
The grinding rate ratio is by the grinding rate of polysilicon film or silicon nitride film is calculated divided by the grinding rate of silicon oxide film.It is the results are shown in table 1 and the table 2.
[table 1]
[table 2]
3.4 embodiment 1 to 8, comparative example 1 to 10
Embodiment 1 to 8, comparative example 1 to 10 are the examples that the composition or the concentration of aqueous dispersion for chemical mechanical polishing have been carried out partial alteration as described in table 1 and the table 2.In table 1 and the table 2, result of the test is also illustrated in the lump.
In the aqueous dispersion for chemical mechanical polishing of embodiment 1 to 8, the grinding rate of polysilicon film and silicon oxide film when the grinding rate of silicon nitride film and silicon oxide film than all in 0.9～1.1 scope.In addition, grinding rate all is more than 20nm/ minute for film arbitrarily, has enough nonferromagnetic substances as aqueous dispersion for chemical mechanical polishing.So as can be known, if use the aqueous dispersion for chemical mechanical polishing of embodiment 1 to 8, to with polysilicon film, silicon nitride film and silicon oxide film as being carried out cmp by the semiconductor device of abradant surface, then any film can be side by side ground with roughly the same grinding rate.
Comparative example 1 is the example that the addition of colloidal silica is made as 5 quality %.Because it is big that mechanical abrasive action becomes, make the grinding rate of silicon oxide film increase, therefore can't use.
Comparative example 2 is the examples that the addition of colloidal silica are made as 0.09 quality %.Grinding rate to any film all reduces, can't be practical, thereby can't use.
Comparative example 3 is the examples that the addition of acid ammonium salt are made as 4 quality %.Because therefore the balance of forfeiture grinding rate ratio can't be used.
Comparative example 4 is the examples that the addition of acid ammonium salt are made as 0.09 quality %.Grinding rate to any film all reduces, can't be practical, thereby can't use.
Comparative example 5 is mass ratio (A)/(B) to be made as 4 example.Because it is big that mechanical abrasive action becomes, the grinding rate of silicon oxide film is increased, therefore can't use.
Comparative example 6 is mass ratio (A)/(B) to be made as 0.5 example.Because therefore the balance of forfeiture grinding rate ratio can't be used.
Comparative example 7 has been to use the example that average grain diameter is made as the colloidal silica of 180nm.Because it is big that mechanical abrasive action becomes, the grinding rate of silicon oxide film is increased, therefore can't use.
Comparative example 8 has been to use the example that average grain diameter is made as the colloidal silica of 9nm.Grinding rate to any film all reduces, can't be practical, thereby can't use.
Comparative example 9 is that the pH with aqueous dispersion for chemical mechanical polishing is made as 3.5 example.Because with respect to the grinding rate of polysilicon film, the grinding rate of silicon nitride film and silicon oxide film is excessive, therefore can't use.
Comparative example 10 is that the pH with aqueous dispersion for chemical mechanical polishing is made as 5.6 example.Because with respect to the grinding rate of polysilicon film, the grinding rate of silicon nitride film and silicon oxide film is too small, therefore can't use.
As mentioned above, if the aqueous dispersion for chemical mechanical polishing of comparative example 1 to 10, then can't realize the purpose of the present application.
3.5 experimental example
3.5.1 first experimental example
The evaluation substrate that has silicon nitride film 20 and silicon oxide film 30 both sides in by abradant surface is to grind in advance in advance with wafer 100 by the commercially available test that will imbed silicon nitride film 20 in inside to obtain.With in the wafer 100, used Sematech 864 (SEMATECH corporate system) in test.Fig. 1 represents to test the profile with wafer 100.The thickness of silicon oxide film 30 is 500nm, and the thickness of silicon nitride film 20 is 150nm.Test is used JSR corporate system CMS4301 and 4302 with following＜grinding condition 2 in advance with wafer 100〉grind.As shown in Figure 2, under the remaining state that 50nm silicon oxide film 30 arranged on the silicon nitride film 20, finish pre-the grinding, obtained estimating and used substrate.
Test after the pre-grinding with wafer 100, is used light interference type film thickness gauge " NanoSpec6100 ", instrumentation be present in the thickness of the silicon oxide film 30 on the silicon nitride film 20 in the pattern 100 μ m spacings, its result is that the thickness of silicon oxide film 30 is 60nm.Then, use contact pin type ladder difference determinator " HRP240 ", measured the ladder residual quantity of silicon oxide film 30, its result is, do not see that ladder is poor, confirms it is smooth basically as shown in Figure 2.
＜grinding condition 2 〉
Lapping device: (strain) ebara corporatlon system, model " EPO-112 "
Grinding pad: Rodel Nitta (strain) system, " IC1000/K-Groove "
Aqueous dispersion for chemical mechanical polishing feed speed: 200mL/ minute
Platform rotating speed: 100rpm
Grinding head rotating speed: 107rpm
Grinding head pushing pressure: 5.0psi
Then, use the aqueous dispersion for chemical mechanical polishing of embodiment 1, under the grinding condition identical, carried out grinding in 90 seconds with embodiment 1.After the grinding, the thickness of the silicon oxide film 30 on the silicon nitride film 20 in the pattern 100 μ m spacings is 0nm.In addition, the amount of recess of the silicon oxide film 30 in the pattern 100 μ m spacings is 2nm.So confirm, silicon nitride film 20 and silicon oxide film 30 are flattened as shown in Figure 3 basically.
3.5.2 second experimental example
The evaluation substrate that has polysilicon film 40 and silicon oxide film 30 both sides in by abradant surface is to grind in advance in advance with wafer 200 by the commercially available test that will imbed polysilicon film 40 in inside to obtain.With in the wafer 200, used SKW 3PS (SKW corporate system) in test.Fig. 4 represents to test the profile with wafer 200.The thickness of polysilicon film 40 is 600nm, and the thickness of silicon oxide film 30 is 400nm.Test is used the polysilicon grinding composition of using always in advance with wafer 200, at following＜grinding condition 3〉under grind.As shown in Figure 5, under the remaining state that 50nm polysilicon film 40 arranged on the silicon oxide film 30 of protuberance, finish pre-the grinding, obtained estimating and used substrate.
Test after the pre-grinding with wafer 100, is used light interference type film thickness gauge " NanoSpec6100 ", instrumentation be present in the thickness of the polysilicon film 40 on the silicon oxide film 30 in the pattern 100 μ m spacings, its result is that the thickness of polysilicon film 40 is 50nm.Then, use contact pin type ladder difference determinator " HRP240 ", measured the ladder residual quantity of polysilicon film 40, its result is, do not see that ladder is poor, confirms it is smooth basically as shown in Figure 5.
＜grinding condition 3 〉
Lapping device: (strain) ebara corporatlon system, model " EPO-112 "
Grinding pad: Rodel Nitta (strain) system, " IC1000/K-Groove "
Aqueous dispersion for chemical mechanical polishing feed speed: 200mL/ minute
Platform rotating speed: 50rpm
Grinding head rotating speed: 55rpm
Grinding head pushing pressure: 4.2psi
Then, use the aqueous dispersion for chemical mechanical polishing of embodiment 1, under the grinding condition identical, carried out grinding in 90 seconds with embodiment 1.After the grinding, the thickness of the polysilicon film 40 on the silicon oxide film 30 in the pattern 100 μ m spacings is 0nm.In addition, the amount of recess of the silicon oxide film 30 in the pattern 100 μ m spacings is 4nm.So confirm, silicon oxide film 30 and polysilicon film 40 are flattened as shown in Figure 6 basically.
The result of first experimental example and second experimental example shows, if use the aqueous dispersion for chemical mechanical polishing of the present application, the substrate that has polysilicon film, silicon nitride film and three kinds of films of silicon oxide film in by abradant surface is ground, then, therefore can not produce hollowly with its planarization owing to can grind with roughly the same speed for any film.
Claims (1)
1. chemical and mechanical grinding method, it is characterized in that, use aqueous dispersion for chemical mechanical polishing, simultaneously to by being selected from polysilicon film, in silicon nitride film and the silicon oxide film carry out cmp more than 2 kinds the time, make described polysilicon film, the grinding rate of described silicon nitride film and described silicon oxide film was more than 20nm/ minute, the grinding rate that makes described polysilicon film and described silicon oxide film is than being polysilicon film/silicon oxide film and described silicon nitride film and the grinding rate ratio of described silicon oxide film is that silicon nitride film/silicon oxide film is 0.9～1.1, wherein
Described aqueous dispersion for chemical mechanical polishing, pH is 4～5, contains:
0.1 the A of～4 quality %: have 10nm～100nm average grain diameter colloidal silica and
0.1 the B of～3 quality %: be selected from least a in ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the ammonium hydrogen sulfate, and,
The mass ratio A/B of described A composition and described B composition is 1～3.
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| JP2007074537A JP4614981B2 (en) | 2007-03-22 | 2007-03-22 | Chemical mechanical polishing aqueous dispersion and semiconductor device chemical mechanical polishing method |
| JP074537/2007 | 2007-03-22 | ||
| PCT/JP2008/052802 WO2008114563A1 (en) | 2007-03-22 | 2008-02-20 | Aqueous dispersion for chemical mechanical polishing and method of chemical mechanical polishing of semiconductor device |
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| US (1) | US20090325383A1 (en) |
| EP (1) | EP2128893A4 (en) |
| JP (1) | JP4614981B2 (en) |
| KR (1) | KR101473501B1 (en) |
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| US8506359B2 (en) * | 2008-02-06 | 2013-08-13 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
| WO2009104517A1 (en) * | 2008-02-18 | 2009-08-27 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
| WO2009104334A1 (en) * | 2008-02-18 | 2009-08-27 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
| US8652350B2 (en) * | 2008-02-27 | 2014-02-18 | Jsr Corporation | Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method using the same, and method of recycling chemical mechanical polishing aqueous dispersion |
| JP5472585B2 (en) | 2008-05-22 | 2014-04-16 | Ｊｓｒ株式会社 | Chemical mechanical polishing aqueous dispersion and chemical mechanical polishing method |
| KR101538826B1 (en) | 2008-10-20 | 2015-07-22 | 니타 하스 인코포레이티드 | Composition for polishing silicon nitride and method for controlling selectivity using same |
| US8480920B2 (en) * | 2009-04-02 | 2013-07-09 | Jsr Corporation | Chemical mechanical polishing aqueous dispersion, method of preparing the same, chemical mechanical polishing aqueous dispersion preparation kit, and chemical mechanical polishing method |
| MY156687A (en) * | 2009-06-22 | 2016-03-15 | Cabot Microelectronics Corp | Cmp compositions and method for suppressing polysilicon removal rates |
| JP5709752B2 (en) | 2009-08-19 | 2015-04-30 | 出光興産株式会社 | Aromatic amine derivative and organic electroluminescence device using the same |
| US8497210B2 (en) * | 2010-10-04 | 2013-07-30 | International Business Machines Corporation | Shallow trench isolation chemical mechanical planarization |
| US20130061876A1 (en) * | 2011-09-14 | 2013-03-14 | Taiwan Semiconductor Manufacturing Company, Ltd. | Semiconductor Device Surface Clean |
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| US9303187B2 (en) * | 2013-07-22 | 2016-04-05 | Cabot Microelectronics Corporation | Compositions and methods for CMP of silicon oxide, silicon nitride, and polysilicon materials |
| JP6160579B2 (en) * | 2014-08-05 | 2017-07-12 | 信越半導体株式会社 | Final polishing method for silicon wafer |
| KR101628878B1 (en) * | 2015-09-25 | 2016-06-16 | 영창케미칼 주식회사 | Cmp slurry composition and polishing method using the same |
| KR102509260B1 (en) * | 2015-11-20 | 2023-03-14 | 삼성디스플레이 주식회사 | Polishing slurry for silicon, method of polishing polysilicon and method of manufacturing a thin film transistor substrate |
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| TWI435381B (en) | 2014-04-21 |
| KR20090122172A (en) | 2009-11-26 |
| TW200839864A (en) | 2008-10-01 |
| US20090325383A1 (en) | 2009-12-31 |
| EP2128893A4 (en) | 2011-05-18 |
| KR101473501B1 (en) | 2014-12-16 |
| JP4614981B2 (en) | 2011-01-19 |
| WO2008114563A1 (en) | 2008-09-25 |
| EP2128893A1 (en) | 2009-12-02 |
| CN101542690A (en) | 2009-09-23 |
| JP2008235652A (en) | 2008-10-02 |
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